CN105523972A - Oxidation method for thioether - Google Patents

Oxidation method for thioether Download PDF

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CN105523972A
CN105523972A CN201410514186.2A CN201410514186A CN105523972A CN 105523972 A CN105523972 A CN 105523972A CN 201410514186 A CN201410514186 A CN 201410514186A CN 105523972 A CN105523972 A CN 105523972A
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hts
procedure
liquid mixture
reaction
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CN105523972B (en
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林民
史春风
朱斌
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses an oxidation method for thioether. The method comprises the step of subjecting a liquid mixture and a titanium-silicate molecular sieve to contacting under the condition of oxidation reaction, wherein the liquid mixture comprises thioether, at least one oxidant, at least one alkaline substance and at least one optional solvent; and when selectivity of a target oxidation product is lower than an expected value, the method also comprises the steps of improving the quality of the alkaline substance in the liquid mixture and optionally improving the quality of the oxidant in the liquid mixture. The method provided by the invention can maintain the selectivity of the target oxidation product at a high level for a long time, effectively prolong the single-way service life of the titanium-silicon molecular sieve used as a catalyst, and reduce regeneration frequency of the catalyst.

Description

A kind of sulfide oxidation method
Technical field
The present invention relates to a kind of sulfide oxidation method.
Background technology
Sulfoxides is important sulfocompound, if dimethyl sulfoxide (DMSO) (DMSO) is a kind of organic compounds containing sulfur, is colourless transparent liquid under normal temperature, has the characteristics such as high polarity, high-hygroscopicity, flammable and high boiling point be non-proton.Dimethyl sulfoxide (DMSO) is water-soluble, ethanol, acetone, EC, is the inert solvent that polarity is strong, is widely used as solvent and reaction reagent.And, dimethyl sulfoxide (DMSO) has very high selective extraction method ability, can be used as the Extraction solvent that alkane is separated with aromatic hydrocarbon, such as: dimethyl sulfoxide (DMSO) can be used for the extracting of aromatic hydrocarbons or divinyl, as process solvent and the solvent that reels off raw silk from cocoons in acrylonitrile polymerization reaction, as synthetic and the solvent that reels off raw silk from cocoons of urethane, as the synthetic of polymeric amide, fluoroaluminate glasses, polyimide and polysulfones.Meanwhile, in medicine industry, dimethyl sulfoxide (DMSO) not only directly as raw material and the carrier of some drugs, and can also play the effects such as anti-inflammatory analgetic, diuresis, calmness, and therefore the active ingredient of Chang Zuowei analgesic drug product makes an addition in medicine.In addition, dimethyl sulfoxide (DMSO) also can be used as capacitor dielectric, frostproofer, brake solution, rare metal extracting agent etc.
At present, sulfoxide generally adopts sulfide oxidation method to obtain, and operable oxygenant comprises nitric acid, superoxide and ozone etc.
When adopting oxygenant (particularly superoxide) by sulfide oxidation, if use HTS as catalyzer, the transformation efficiency of oxygenant and the selectivity of desirable oxidation product can be improved.But with the prolongation in reaction times, the catalytic performance of HTS can be on a declining curve, oxygenant transformation efficiency and/or desirable oxidation selectivity of product is caused to reduce.When react carry out in fixed-bed reactor time, because titanium molecular sieve catalysis performance reduces, need HTS to regenerate in reactor or outside reactor, cause reactor down-time, thus affect production efficiency and improve the running cost of device.
When the catalyzer of regeneration puts into operation again, when particularly again putting into operation after reaction in-situ regeneration, the Activity Fluctuation of catalyzer is larger, need could stablize for a long time, desirable oxidation selectivity of product is caused to reduce, this not only can reduce the running efficiency of device, but also needs later separation purification procedures to adjust operational condition, adds the complicacy of operation; Meanwhile, also need to combine the smooth running that operations such as improving temperature of reaction carrys out realization response, but these measures often accelerator activator inactivation.
Therefore, for reacting using HTS as the sulfide oxidation of catalyzer, how to extend the one way work-ing life of the HTS as catalyzer, reducing regeneration frequency is enhance productivity and one of key link reducing running cost.
Summary of the invention
The present invention is intended to the sulfide oxidation reaction above shortcomings solved using HTS as catalyzer, a kind of sulfide oxidation method is provided, the method can extend the one way work-ing life of the HTS as catalyzer effectively, in continuous run in long period process, desirable oxidation selectivity of product can be stabilized in higher level.
The invention provides a kind of sulfide oxidation method, under the method is included in oxidation reaction condition, a kind of liquid mixture is contacted with HTS, described liquid mixture contains thioether, at least one oxygenant, at least one alkaline matter and optional at least one solvent, wherein, desirable oxidation selectivity of product drop to satisfy condition 1 time, the method also comprises carries out set-up procedure, until desirable oxidation selectivity of product rises to when satisfying condition 2, stop described set-up procedure
Desirable oxidation selectivity of product S under condition 1, sometime t twith initial target oxidation products selectivity S 0ratio S t/ S 0be 0.85≤S t/ S 0<1;
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation products selectivity S 0ratio S '/S 0be 0.9≤S '/S 0≤ 1;
Described set-up procedure is the combination of set-up procedure A or set-up procedure A and set-up procedure B,
Set-up procedure A: the quality improving described liquid mixture neutral and alkali material;
Set-up procedure B: the quality improving oxygenant in described liquid mixture.
According to sulfide oxidation method of the present invention, in long-time continuous operational process, when the desirable oxidation selectivity of product that the reaction mixture exported by reactor is determined is lower than desired value, carry out set-up procedure, namely improve the quality as the liquid mixture neutral and alkali material of charging and the optional quality improved as oxygenant in the liquid mixture of charging, the desirable oxidation selectivity of product originally presenting downtrending can be made to go up.In long-time continuous operational process, desirable oxidation selectivity of product can be maintained higher level all the time like this, avoid needing in later separation purge process to adjust operational condition according to the composition of reaction mixture on the one hand; Then effectively extend the one way work-ing life of the HTS as catalyzer on the other hand, reduce the regeneration frequency of catalyzer, extend the parallel-adder settle-out time of device.
Embodiment
The invention provides a kind of sulfide oxidation method, under the method is included in oxidation reaction condition, contacted with HTS by a kind of liquid mixture, described liquid mixture contains thioether, at least one oxygenant, at least one alkaline matter and optional at least one solvent.
In the present invention, " at least one " represents one or more (as two or more); " optionally " represents containing or does not contain.
Described oxygenant can be that commonly use various can by the material of sulfide oxidation.Preferably, described oxygenant is superoxide.Described superoxide refers to the compound containing-O-O-key in molecular structure, can be selected from hydrogen peroxide, organo-peroxide and peracid.Described organo-peroxide refers to that one or two hydrogen atom in hydrogen peroxide molecule is replaced by organic group and the material obtained.Described peracid refers to the organic oxacid containing-O-O-key in molecular structure.The specific examples of described superoxide can include but not limited to: hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid.Preferably, described oxygenant is hydrogen peroxide, can reduce separation costs further like this.The hydrogen peroxide existed in a variety of manners that described hydrogen peroxide can be commonly used for this area.
From the angle improved further according to the security of method of the present invention, preferably use the hydrogen peroxide existed as an aqueous solution according to method of the present invention.The concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, such as: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method to prepare, and also can be commercially available, such as: can for can be commercially available the hydrogen peroxide of 30 % by weight, the hydrogen peroxide of 50 % by weight or 70 % by weight hydrogen peroxide.
The consumption of described oxygenant can be selected according to the oxidation products of expection, is not particularly limited.Usually, the mol ratio of oxygenant and thioether can in the scope of 0.1-5:1.From the optionally angle improved further for sulfoxide, the mol ratio of oxygenant and thioether preferably in the scope of 0.1-2:1, more preferably in the scope of 0.2-1:1.
According to method of the present invention, adopt the catalyzer that HTS is reacted as thioether and oxidising agent.Described HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in lattice framework, can use chemical formula xTiO 2siO 2represent.The present invention is not particularly limited for the content of titanium atom in HTS, can be that the routine of this area is selected.Particularly, x can be 0.0001-0.05, is preferably 0.01-0.03, is more preferably 0.015-0.025.
Described HTS can for the common HTS with various topological framework, such as: described HTS can be selected from the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure, the HTS of two dimension hexagonal structure is (as Ti-MCM-41, and the HTS of other structure (as Ti-ZSM-48) etc. Ti-SBA-15).Described HTS is preferably selected from the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure, is more preferably the HTS of MFI structure.
According to method of the present invention, described HTS is preferably hollow HTS, can obtain better catalytic effect like this.Described hollow HTS is the HTS of MFI structure, and the crystal grain of this HTS is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P 0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Described hollow HTS can be commercially available (be such as purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd be the molecular sieve of HTS), also method can prepare disclosed in CN1132699C.
According to method of the present invention, the contact form of described HTS and described liquid mixture is not particularly limited, can HTS be seated in the beds of fixed-bed reactor, make described liquid mixture by described beds, thus realize, under HTS exists, thioether and oxidising agent being reacted; Also described liquid mixture and HTS can be mixed to form slurry, thus realize, under HTS exists, thioether and oxidising agent being reacted.
When described liquid mixture and HTS are mixed to form slurry, can adopt various method that slurry is carried out solid-liquor separation after contact reacts completes, thus obtain the liquid material containing desirable oxidation product.Such as: by membrane separation unit, described liquid material can be carried out solid-liquor separation.
Time in the beds described HTS being seated in fixed-bed reactor, the quantity of described beds can be one or more.When the quantity of beds is multiple, for being positioned at the different zones of a reactor, also multiple reactor can be arranged in.
In one embodiment of the invention, described beds contains the first beds and the second beds, described liquid mixture flows through the first beds and the second beds successively, namely with the flow direction of described liquid mixture for benchmark, described first beds is positioned at the upstream of described second beds.Described first beds can, for identical, also can be different with the kind of the HTS of loading in described second beds.Preferably, the HTS of described first beds filling is hollow HTS, the HTS of described second beds filling is the HTS except hollow HTS, as one or more in the HTS (such as HTS Ti-MCM-41) of the HTS (such as titanium-silicon molecular sieve TS-1) of other MFI structure, two-dimentional hexagonal structure and the HTS (such as HTS Ti-Beta) of BEA structure, the deactivation rate of HTS can be delayed so further.More preferably, the HTS of described first beds filling is hollow HTS, the HTS of described second beds filling is titanium-silicon molecular sieve TS-1, can obtain better catalytic effect like this, and extend the one way work-ing life of HTS further.
When described beds contains the first beds and the second beds, the weight ratio of the HTS of loading in the HTS of loading in described first beds and described second beds can be 0.5-20:1, be preferably 1-20:1, more preferably 2-10:1.
When described beds contains the first beds and the second beds, described first beds and the second beds can contain one or more beds separately.When the first beds and/or the second beds contain multiple beds, can for being connected in series between multiple beds, also can for being connected in parallel, can also be series connection and combination in parallel, such as: multiple beds is divided into many groups, beds often in group for being connected in series and/or being connected in parallel, for being connected in series and/or being connected in parallel between each group.Described first beds and described second beds can be arranged on the different zones of same reactor, also can be arranged in different reactors.
When described beds contains the first beds and the second beds, it can, for identical, also can be different that described liquid mixture flows through the first beds with the superfacial velocity of the second beds.Preferably, described liquid mixture flows through the superfacial velocity of the first beds is v 1, the superfacial velocity flowing through the second beds is v 2, wherein, v 1< v 2, the one way work-ing life of HTS can be extended so further.More preferably, v 2/ v 1=1.5-10.Further preferably, v 2/ v 1=2-5.
In the present invention, described superfacial velocity (flow velocity) to refer in the unit time by the area of the mass rate (in kg/s) of the liquid mixture of beds whole process and a certain cross section of beds (with m 2meter) ratio.The quality of the liquid mixture of fixed-bed reactor can will be sent into as " by the mass rate of the liquid mixture of whole beds in the unit time " in unit time.In the present invention, particular requirement be there is no for the superfacial velocity of liquid mixture in the first beds, generally can at 0.001-200kg/ (m 2s) in scope.
Various method can be adopted to regulate the superfacial velocity of described liquid mixture in the first beds and the second beds.Such as, the superfacial velocity of regulates liquid mixture can be carried out by the cross-sectional area of selecting catalyst bed.Particularly, the cross-sectional area of described first beds can be made to be greater than the cross-sectional area of described second beds, thus to make v 1< v 2.Particularly, the internal diameter of described first beds is D 1, the internal diameter of described second beds is D 2, wherein, D 1> D 2, D 1/ D 2be preferably 1.5-10, be more preferably 2-5.Superfacial velocity according to expection determines that the method for the cross-sectional area of beds is known in those skilled in the art, no longer describes in detail herein.
When described beds contains the first beds and the second beds, the residence time of described liquid mixture in the first beds is T 1, the total residence time in beds is T, usually, and T 1/ T=0.2-0.96, preferably, T 1/ T=0.3-0.95.More preferably, T 1/ T=0.5-0.85, can obtain the catalyzer one way work-ing life extended further like this, can also obtain better reaction effect simultaneously.
According to method of the present invention, when beds contains the first beds and the second beds, material can be supplemented as the case may be between the first beds and the second beds, when the first beds and/or the second beds are multiple beds, fresh material can be supplemented between the first beds and/or between the second beds in described liquid mixture as the case may be.Such as: between the first beds and the second beds, between the first beds and/or between the second beds, supplement thioether, oxygenant and/or solvent.But, it should be noted that, (namely described liquid mixture flows through whole beds of the first beds, the whole process of the first beds) and the second beds whole beds (namely, the whole process of the second beds), described liquid mixture not included in the fresh material introduced between the first beds, between the second beds and between the first beds and the second beds, previously described superfacial velocity is determined by described liquid mixture, is not subject to the impact whether introducing fresh material.
According to method of the present invention, beds only can load HTS, also can contain HTS and inactive filler.In beds, load inactive filler to adjust the amount of HTS in beds, thus the speed of reaction is regulated.When described beds contains HTS and inactive filler, in beds, the content of inactive filler can be 5-95 % by weight.Described inactive filler refers to the filler not having or substantially do not have catalytic activity to oxidizing reaction, and its specific examples can include but not limited to: one or more in quartz sand, ceramic ring and potsherd.
According to method of the present invention, described HTS can be the former powder of HTS, also can be shaping HTS, is preferably shaping HTS.Shaping HTS is generally containing the HTS as activeconstituents and the carrier as binding agent, and wherein, the content of HTS can be conventional selection.Usually, with the total amount of described shaping HTS for benchmark, the content of HTS can be 5-95 % by weight, is preferably 10-95 % by weight, is more preferably 70-90 % by weight; The content of described carrier can be 5-95 % by weight, is preferably 5-90 % by weight, is more preferably 10-30 % by weight.The carrier of described shaping HTS can be conventional selection, as aluminum oxide and/or silicon oxide.The method preparing described shaping HTS is known in the field, no longer describes in detail herein.The granular size of described shaping HTS is also not particularly limited, and can carry out appropriate selection according to concrete shape.Particularly, the median size of described shaping HTS can be 4-10000 micron, is preferably 5-5000 micron, is more preferably 40-4000 micron, as 50-1000 micron.Described median size is volume average particle size, and laser particle analyzer can be adopted to measure.
In the various reactions adopting HTS as catalyzer (referring generally to the reaction of non-sulfide oxidation) device, as Ammoximation reaction, in hydroxylating and epoxidation reaction device, usually after plant running for some time, the catalytic activity of catalyzer declines, need to carry out in device or ex-situ regeneration, even if when carry out regenerating also be difficult to obtain satisfied active time, catalyzer is needed to draw off (namely from device, more catalyst changeout), and the catalyzer drawn off (namely, drawing off agent or spent catalyst) current treatment process normally piles up and buries, occupy valuable land resources and inventory space on the one hand, HTS production cost is higher on the other hand, directly pass into disuse and also result in great waste.
The present inventor finds in research process, regenerates if these are drawn off agent, using the catalyzer that the regenerator obtained uses in the inventive method, still can obtain high catalytic activity.
According to method of the present invention, at least part of HTS be preferably through regeneration the reaction unit using HTS as catalyzer draw off agent.Described draw off agent can for from various use HTS as the agent that draws off drawn off the device of catalyzer, such as can for draw off from oxidation reaction apparatus draw off agent.Described oxidizing reaction can be various oxidizing reaction, draw off such as agent can for Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off in agent one or more, be specifically as follows cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draw off agent and propylene ring oxidation reaction device draw off in agent one or more.
Being not particularly limited drawing off the condition that agent carries out regenerating, appropriate selection can being carried out according to the source drawing off agent, such as: high-temperature roasting and/or solvent wash.
The activity drawing off agent through regeneration is different according to its source.Usually, the activity drawing off agent through regeneration can be the 5-95% of its activity (that is, the activity of fresh dose) when fresh.Preferably, the activity drawing off agent through regeneration can be the 10-90% of its activity when fresh, more preferably the 10-60% of its activity when fresh.When the activity drawing off agent through regeneration is the 10-60% of its activity when fresh, gratifying desirable oxidation selectivity of product can not only be obtained, and the oxygenant effective rate of utilization improved further can be obtained.Under the prerequisite taking into account oxygenant effective rate of utilization, from the angle improving further desirable oxidation selectivity of product, the activity drawing off agent through regeneration is the 30-55% of its activity when fresh.The activity of described fresh titanium si molecular sieves is generally more than 95%.
Described activity measures by the following method: will draw off through regeneration the catalyzer that agent and fresh dose are used as cyclohexanone oxamidinating reaction respectively, the condition of this Ammoximation reaction is: catalyzer (in HTS), 36 % by weight ammoniacal liquor (with NH 3meter), the hydrogen peroxide of 30 % by weight is (with H 2o 2meter), the trimethyl carbinol and pimelinketone 1:7.5:10:7.5:10 in mass ratio, at atmosheric pressure in 80 DEG C of reaction 2h.Calculate with the transformation efficiency drawing off pimelinketone when agent and fresh dose are catalyzer through regeneration respectively, and it can be used as the activity drawing off agent and fresh dose through regeneration, wherein, transformation efficiency=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100% of pimelinketone.
Be that when drawing off agent through the reaction unit of regeneration, with the total amount of described catalyzer for benchmark, the content that the reaction unit through regeneration draws off agent is preferably more than 5 % by weight, can obtain higher oxygenant effective rate of utilization like this at least part of catalyzer.According to method of the present invention, even if all catalyzer is when the reaction unit of regeneration draws off agent, still higher catalytic activity can be obtained.
According to method of the present invention, described HTS is as catalyzer, and its consumption is as the criterion can realize catalysis, is not particularly limited.Can select according to the contact form of HTS and described liquid mixture.Such as, when HTS and described liquid mixture are mixed to form slurry, the weight ratio of thioether and HTS can be 0.1-50:1, is preferably 1-50:1, as 1-25:1; Time in beds HTS being seated in fixed-bed reactor, the weight hourly space velocity of described thioether can be 0.05-100h -1, be preferably 0.1-50h -1(as 2-20h -1).In the present invention, weight hourly space velocity with the total amount of HTS in whole beds for benchmark.
According to method of the present invention, described liquid mixture contains at least one alkaline matter, can improve the selectivity for sulfoxide so further.Described alkaline matter refer to the pH value of its aqueous solution be greater than 7 material.The specific examples of described alkaline matter can include but not limited to: ammonia (that is, NH 3), amine, quaternary ammonium hydroxide and M 1(OH) n(wherein, M 1for basic metal or alkaline-earth metal, n is and M 1the identical integer of valency).
As described alkaline matter, ammonia can be introduced with the form of liquefied ammonia, also can introduce as an aqueous solution, can also introduce with the form of gas.Concentration as the ammonia (that is, ammoniacal liquor) of aqueous solution form is not particularly limited, and can be conventional selection, such as 1-36 % by weight.
As described alkaline matter, amine refers to hydrogen partial on ammonia or is all replaced the material formed by alkyl, comprises primary amine, secondary amine and tertiary amine.Described amine is specifically as follows the material shown in formula I and/or C 3-C 11heterocyclic amine,
In formula I, R 1, R 2and R 3can be H or C separately 1-C 6alkyl (as C 1-C 6alkyl), and R 1, R 2and R 3be asynchronously H.Herein, C 1-C 6alkyl comprise C 1-C 6straight chained alkyl and C 3-C 6branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl and n-hexyl.
The specific examples of amine can include but not limited to: methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, Tri N-Propyl Amine, di-n-propylamine, Tri-n-Propylamine, Isopropylamine, Diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, sec-butylamine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, isobutylcarbylamine, di-iso-amylamine, tri-isoamylamine, tertiary amylamine, normal hexyl Amine and n-octyl amine.
Described heterocyclic amine is compound finger ring having nitrogen-atoms and this nitrogen-atoms has lone-pair electron.Described heterocyclic amine can be such as one or more in substituted or unsubstituted pyrroles, substituted or unsubstituted Pyrrolidine, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substituted or unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substituted or unsubstituted dihydroquinoline, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinoline 99.9 and substituted or unsubstituted pyrimidine.
As described alkaline matter, quaternary ammonium hydroxide is specifically as follows the material shown in formula II,
In formula II, R 4, R 5, R 6and R 7can be C separately 1-C 6alkyl (as C 1-C 6alkyl).Described C 1-C 6alkyl comprise C 1-C 6straight chained alkyl and C 3-C 6branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, tert-pentyl and n-hexyl.
The specific examples of described quaternary ammonium hydroxide can include but not limited to: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH (comprising four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), TBAH (comprising 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl-ammonium hydroxide and tetra-tert ammonium hydroxide) and four pentyl ammonium hydroxide.
As described alkaline matter, M 1(OH) nfor the oxyhydroxide of alkali-metal oxyhydroxide or alkaline-earth metal, such as, can be sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydrated barta and calcium hydroxide.
According to method of the present invention, described alkaline matter can directly use, and uses after also described alkaline matter can being mixed with solution.
According to method of the present invention, the consumption of described alkaline matter can be selected according to the composition of liquid mixture.Usually, the mol ratio of described alkaline matter and thioether can in the scope of 0.00001-0.1:1, preferably in the scope of 0.00002-0.05:1, more preferably in the scope of 0.00005-0.005:1.
According to method of the present invention, described liquid mixture can contain solvent, also can not contain solvent.Preferably, described liquid mixture contains at least one solvent, can control speed and the severe degree of reaction so better.The present invention is not particularly limited for the kind of described solvent, and described solvent can for all kinds of SOLVENTS conventional in sulfide oxidation reaction.Preferably, described solvent is water, C 1-C 10alcohol, C 3-C 10ketone, C 2-C 10nitrile and C 1-C 6carboxylic acid at least one.Preferably, described solvent is water, C 1-C 6alcohol, C 3-C 8ketone and C 2-C 5nitrile in one or more.More preferably, described solvent is one or more in water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol and acetone.Further preferably, described solvent is one or more in water, methyl alcohol, acetone and the trimethyl carbinol.
The present invention is not particularly limited for the consumption of described solvent, can select according to the amount of thioether and oxygenant.Usually, the mol ratio of described solvent and described thioether can be 1-100:1, is preferably 2-80:1 (as 5-40:1).
According to method of the present invention, described thioether can be the various compounds containing-S-key, and preferred described thioether is selected from the thioether that carbonatoms is 2-18, is more preferably dimethyl thioether and/or thioanisole.
According to method of the present invention, desirable oxidation selectivity of product drop to satisfy condition 1 time, the method also comprises carries out set-up procedure, until desirable oxidation selectivity of product rises to when satisfying condition 2, stops described set-up procedure,
Desirable oxidation selectivity of product S under condition 1, sometime t twith initial target oxidation products selectivity S 0ratio S t/ S 0be 0.85≤S t/ S 0<1;
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation products selectivity S 0ratio S '/S 0be 0.9≤S '/S 0≤ 1;
Described set-up procedure is the combination of set-up procedure A or set-up procedure A and set-up procedure B,
Set-up procedure A: the quality improving described liquid mixture neutral and alkali material;
Set-up procedure B: the quality improving oxygenant in described liquid mixture.
According to method of the present invention, satisfy condition 2 time, stop improve as the liquid mixture neutral and alkali material of charging quality and the quality of alkaline matter is remained numerical value when satisfying condition 2; In method of the present invention, when also comprising set-up procedure B, satisfy condition 2 time, stop improving the quality of oxygenant in liquid mixture and the quality of oxygenant remained numerical value when satisfying condition 2.
Described set-up procedure is carried out when meeting above-mentioned condition 1, the desirable oxidation selectivity of product originally presenting downtrending can be made to go up, desirable oxidation selectivity of product is promoted to higher level, thus extend the one way work-ing life of HTS, and desirable oxidation selectivity of product is maintained higher level for a long time.
Under the prerequisite in one way work-ing life that can extend HTS, from the angle of further extension fixture parallel-adder settle-out time, in condition 1, S t/ S 0<0.9.
In the present invention, the desirable oxidation selectivity of product=mole number of the thioether of the mole number/participation reaction of desirable oxidation product (in the reaction mixture obtained) × 100%;
Wherein, the mole number of the thioether in the reaction mixture of the mole number of the thioether of the mole number=add of the thioether of reaction-obtain is participated in.
Desirable oxidation selectivity of product S can be determined by the composition of monitoring the reaction mixture exported from reactor in reaction process continuously 0, S tand S '.When reactor is multiple reactor, with the flow direction of liquid mixture for benchmark, the reaction mixture exported by the reactor being positioned at logistics end is to determine desirable oxidation selectivity of product S 0, S tand S '.
In the present invention, initial target oxidation products selectivity S 0after reactor steady running, determine from the composition of the first batch of reaction mixture of reactor output.Such as, the reaction mixture that reactor steady running can be obtained within 0.5-10 hour is as first batch of reaction mixture.
Ordinary method can be adopted to measure the composition of the reaction mixture exported from reactor, such as vapor-phase chromatography.
Although satisfy condition 1 time, improve the quality of liquid mixture neutral and alkali material or the quality of raising liquid mixture neutral and alkali material and improve the quality of oxygenant in liquid mixture until satisfy condition 2, but in set-up procedure A, preferably improve the quality of liquid mixture neutral and alkali material with the amplitude in 0.01-10%/sky; In set-up procedure B, preferably improve the quality of oxygenant in liquid mixture with the amplitude in 0.02-5%/sky, longer HTS one way work-ing life can be obtained like this, reaction can also be made to carry out more reposefully.In the present invention, " amplitude " refers to the step-length between adjacent two numerical value.
According to method of the present invention, various method can be adopted to improve the quality of liquid mixture neutral and alkali material and oxygenant.Such as: the addition of alkaline matter and oxygenant when preparing described liquid mixture can be improved to improve the quality of liquid mixture neutral and alkali material and oxygenant.When alkaline matter and oxygenant provide respectively in the form of a solution, the quality of liquid mixture neutral and alkali material and oxygenant can be improved by the mode of the concentration of oxygenant in the concentration of raising alkaline substance solution neutral and alkali material and oxidizing agent solution.When the mode of the concentration by improving oxygenant in oxidizing agent solution improves the quality of oxygenant in liquid mixture, the consumption of oxidizing agent solution can remain unchanged, also can correspondingly carry out adjusting (such as, the consumption of corresponding reduction oxidizing agent solution, to keep the constant rate between thioether and oxygenant), as long as can guarantee that the quality of oxygenant in liquid mixture is for improving.In actual mechanical process, at least part of solvent can be mixed with alkaline matter and oxygenant, thus preparation alkaline substance solution and oxidizing agent solution, realize reaction is carried out in the presence of at least one solvent simultaneously.
According to method of the present invention, in long-time continuous operational process, the increase rate of liquid mixture neutral and alkali material mass and the increase rate of optional oxygenant quality can be identical or different.Usually, the amplitude that early stage can be lower in the reaction improves alkaline matter quality and optional oxygenant quality, and the phase can improve alkaline matter quality and optional oxygenant quality with higher amplitude after the reaction.
According to method of the present invention, the maximum value of the quality of liquid mixture neutral and alkali material and the quality of oxygenant can realize desirable oxidation product stable as expection level is as the criterion with the quality of the quality by improving alkaline matter and optional oxygenant respectively.Usually, the maximum mol ratio of described alkaline matter and described thioether can be not higher than 0.1:1, is preferably not higher than 0.05:1.The maximum mol ratio of described oxygenant and thioether can be not higher than 5:1, is preferably not higher than 2:1.
According to method of the present invention, when carrying out set-up procedure, the consumption of rest materials is generally and remains unchanged, and can certainly correspondingly adjust, as long as the quality of liquid mixture neutral and alkali material and the quality of oxygenant are for improving.
According to method of the present invention, described set-up procedure is the combination of set-up procedure A or set-up procedure A and set-up procedure B.
Set-up procedure A can be used alone, that is, satisfy condition 1 time, only can carry out set-up procedure A.
Set-up procedure A also can combinationally use with set-up procedure B.
When set-up procedure A and set-up procedure B is combinationally used, in a first embodiment, satisfy condition 1 time, carry out set-up procedure A and set-up procedure B, now set-up procedure A and set-up procedure B can synchronously carry out, and also can asynchronously carry out, and preferably asynchronously carries out, so more be conducive to operation, be also easier to control reaction simultaneously.
When set-up procedure A and set-up procedure B is combinationally used, in the second embodiment, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, wherein, set-up procedure A is at least one times carried out, as 1-5 (preferred 1-3 time) set-up procedure A between adjacent twice set-up procedure B.That is, 1 is satisfied condition for n time altogether, wherein, n 1secondary satisfy condition 1 time, carry out set-up procedure A, n 2secondary satisfy condition 1 time, carry out set-up procedure B, n 1+ n 2=n, n 1>=n 2, as n 1/ n 2=1-5, preferred n 1/ n 2=1-3.
When set-up procedure A and set-up procedure B is combinationally used, in the third embodiment, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, wherein, set-up procedure B is at least one times carried out, as 1-5 (preferred 1-3 time) set-up procedure B between adjacent twice set-up procedure A.That is, n ' is secondary altogether satisfies condition 1, wherein, and n 1' secondary satisfy condition 1 time, carry out set-up procedure B, n 2' secondary satisfy condition 1 time, carry out set-up procedure A, n 1'+n 2'=n, n 1'>=n 2', as n 1'/n 2'=1-5, preferred n 1'/n 2'=1-3.
Preferably, set-up procedure A and set-up procedure B is combinationally used, like this can one way work-ing life of more effectively extending catalyst, obtain higher desirable oxidation selectivity of product.
According to method of the present invention, described oxidation reaction condition is fixed with desirable oxidation product.Usually, the temperature of beds can be 0-120 DEG C, is preferably 20-80 DEG C.Pressure in reactor can be 0-5MPa, and be preferably 0.5-3.5MPa, described pressure is in gauge pressure.
According to method of the present invention, when described beds comprises previously described first beds and the second beds, the temperature of described first beds and the temperature of described second beds can be identical or different.From the angle of ease-to-operate, the temperature of described first beds is identical with the temperature of described second beds.From further improving desirable oxidation selectivity of product and the angle extending one way work-ing life of HTS further, preferably the temperature of described first beds is the temperature higher than described second beds.More preferably, the temperature of described first beds than the temperature height 5-30 DEG C of described second beds, as 10-20 DEG C.
Can also comprise according to method of the present invention and the reaction mixture exported from fixed-bed reactor is separated, to obtain desirable oxidation product (as sulfoxide) and unreacted reactant.The method being carried out being separated by reaction mixture can be selected for the routine of this area, is not particularly limited.Isolated unreacted reactant can recycle.
Adopt method of the present invention by sulfide oxidation, effectively can extend the one way work-ing life of the HTS as catalyzer, reduce the regeneration frequency of HTS.Method of the present invention is specially adapted to sulfide oxidation to prepare sulfoxide, adopts method of the present invention can obtain the comparatively stable reaction mixture of sulfoxide content, is convenient to the separation and purification of subsequent products.
Describe the present invention in detail below in conjunction with embodiment, but therefore do not limit the scope of the invention.
In following examples and comparative example, titanium-silicon molecular sieve TS-1 used according to Zeolites, the method preparation described in 1992, Vol.12:943-950, its titanium oxide content is 2.5 % by weight; Hollow HTS used is be the hollow HTS of HTS purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd, and its titanium oxide content is 2.5 % by weight.
In following examples and comparative example, agents useful for same is commercially available analytical reagent, and pressure is all in gauge pressure.
In following examples and comparative example, adopt gas-chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate sulfoxide selectivity on this basis respectively, embodiment 11-18 and 21 also calculates oxygenant effective rate of utilization further:
Sulfoxide selectivity=the mole number of the thioether of the mole number/participation reaction of sulfoxide (in the reaction mixture obtained) × 100%;
Oxygenant effective rate of utilization=the mole number of the oxygenant of the mole number/participation reaction of sulfoxide (in the reaction mixture obtained) × 100%.
Wherein, the mole number of remaining thioether in the reaction mixture of the mole number of the thioether of the mole number=add of the thioether of reaction-obtain is participated in;
Participate in the mole number of remaining oxygenant in the reaction mixture of the mole number of the oxygenant of the mole number=add of the oxygenant of reaction-obtain.
Following examples 4,11-18 and 21 adopt following methods to measure the activity of catalyzer:
By catalyzer, 36 % by weight ammoniacal liquor (with NH 3meter), the hydrogen peroxide of 30 % by weight is (with H 2o 2meter), the trimethyl carbinol and pimelinketone in mass ratio=1:7.5:10:7.5:10 mixing after at atmosheric pressure after 80 DEG C of stirring reaction 2h, reactant is filtered, analyze with the composition of vapor-phase chromatography to the liquid phase obtained, adopt the transformation efficiency of following formulae discovery pimelinketone and it can be used as the activity of this catalyzer
The transformation efficiency (%) of pimelinketone=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100%.
Embodiment 1-21 is for illustration of method of the present invention.
Embodiment 1
By catalyzer, (that is, shaping titanium-silicon molecular sieve TS-1, volume average particle size is the spherical catalyst of 500 μm, and in catalyzer, the content of titanium-silicon molecular sieve TS-1 is 80 % by weight, and the content of silicon oxide is 20 % by weight, and density is 0.76g/cm 3) be seated in fixed-bed reactor, form beds, wherein, the quantity of beds is 1 layer.
The liquid mixture formed by dimethyl thioether, the hydrogen peroxide (providing using the form of the hydrogen peroxide of 30 % by weight) as oxygenant, the acetone as solvent and ammoniacal liquor (starting point concentration is 10 % by weight) is sent into from the bottom of fixed-bed reactor and flows through beds.Wherein, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:0.5, and the mol ratio of dimethyl thioether and solvent acetone is 1:10, dimethyl thioether and NH 3initial molar ratio be 1; 0.005, the weight hourly space velocity of dimethyl thioether is 2h -1.Temperature in beds is 45 DEG C, and the pressure in fixed-bed reactor is 0.8MPa.
The composition of the reaction mixture exported from reactor is monitored continuously, at dimethyl sulfoxide (DMSO) selectivity S in reaction process twith initial (reaction proceeds to 0.5 little sampling and measuring constantly) dimethyl sulfoxide (DMSO) selectivity S 0ratio S t/ S 0be 0.85≤S t/ S 0during <0.9 (that is, satisfy condition 1 time), improve NH in liquid mixture with the amplitude in 0.01-10%/sky 3quality (by improving NH in ammoniacal liquor 3concentration realize, simultaneously the consumption of ammoniacal liquor remains unchanged) until dimethyl sulfoxide (DMSO) selectivity S ' and initial dimethyl sulfoxide (DMSO) selectivity S 0ratio S '/S 0be 0.9≤S '/S 0when≤1 (that is, satisfy condition 2 time), stop improving NH in liquid mixture 3quality and numerical value after remaining rising.
Carry out the reaction of 660 hours, at the end of reaction, the concentration of ammoniacal liquor is 29 % by weight.The dimethyl sulfoxide (DMSO) selectivity that the reaction mixture being proceeded to 0.5 hour by reaction and obtained for 660 hours is determined is listed in Table 1.
Comparative example 1
Adopt the method cacodyl oxide base thioether identical with embodiment 1, unlike, do not change liquid mixture neutral and alkali material (that is, NH in reaction process 3) quality.The result of reacting 0.5 hour and 360 hours is listed in Table 1.
Embodiment 2
Adopt the method cacodyl oxide base thioether identical with embodiment 1, unlike, in reaction process, to satisfy condition for the 1st time 1 time, improve NH in liquid mixture with the amplitude in 0.01-10%/sky 3consumption (by improving NH in ammoniacal liquor 3concentration realize, simultaneously the consumption of ammonia soln remains unchanged) until satisfy condition 2 time, stop improving NH in liquid mixture 3consumption and numerical value after remaining rising; To satisfy condition for the 2nd time 1 time, the quality improving hydrogen peroxide in liquid mixture with the amplitude in 0.02-5%/sky (is realized by the concentration improving hydrogen peroxide in hydrogen peroxide, simultaneously the consumption of hydrogen peroxide solution remains unchanged) until satisfy condition 2 time, stop improving the quality of hydrogen peroxide in liquid mixture and the numerical value after remaining rising, the rest may be inferred (namely, odd-times satisfy condition 1 time, improve NH in liquid mixture with the amplitude in 0.01-10%/sky 3quality until satisfy condition 2; Even-times satisfy condition 1 time, improve the quality of hydrogen peroxide in liquid mixture until satisfy condition 2 with the amplitude in 0.02-5%/sky).
Carry out the reaction of 770 hours, at the end of reaction, the concentration of ammoniacal liquor is 20 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 42 % by weight.The result of reacting 0.5 hour and 770 hours is listed in Table 1.
Embodiment 3
Adopt the method cacodyl oxide base thioether identical with embodiment 2, unlike, (that is, shaping hollow HTS, the density of catalyzer is 0.70g/cm in the hollow HTS replacement of the titanium-silicon molecular sieve TS-1 equivalent in catalyzer 3).Carry out the reaction of 770 hours, at the end of reaction, the concentration of ammoniacal liquor is 18 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 39 % by weight.The result of reacting 0.5 hour and 770 hours is listed in Table 1.
Embodiment 4
Adopt the method cacodyl oxide base thioether identical with embodiment 2, unlike, catalyzer is that the preformed catalyst (for volume average particle size is the spherical catalyst of 500 μm) drawn off from cyclohexanone oxamidinating reaction process carries out regenerating and obtains, this catalyzer contains the titanium-silicon molecular sieve TS-1 of 80 % by weight and the silicon oxide of 20 % by weight, and regeneration condition is: at 550 DEG C in air atmosphere roasting 4h.The activity of regenerated catalyst is 50%, and its activity when fresh is 95%.Carry out the reaction of 800 hours, at the end of reaction, the concentration of ammoniacal liquor is 16 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 37 % by weight.The result of reacting 0.5 hour and 800 hours is listed in Table 1.
Embodiment 5
Adopt the method cacodyl oxide base thioether identical with embodiment 2, unlike, under the condition that the total filling amount of shaping HTS is constant, first load shaping hollow HTS (identical with embodiment 3), recharge shaping titanium-silicon molecular sieve TS-1 (identical with embodiment 1), thus formation beds, the i.e. beds of liquid mixture first by being formed by shaping hollow HTS, then the beds by being formed by shaping titanium-silicon molecular sieve TS-1.Wherein, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 2:1.Carry out the reaction of 840 hours, at the end of reaction, the concentration of ammoniacal liquor is 17 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 36 % by weight.The result of reacting 0.5 hour and 840 hours is listed in Table 1.
Embodiment 6
Adopt the method cacodyl oxide base thioether identical with embodiment 5, unlike, under the condition that the total filling amount of shaping HTS is constant, first load shaping titanium-silicon molecular sieve TS-1, to recharge shaping hollow HTS, thus formation beds, wherein, the weight ratio of shaping titanium-silicon molecular sieve TS-1 and shaping hollow HTS is 1:2.Carry out the reaction of 700 hours, at the end of reaction, the concentration of ammoniacal liquor is 24 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 45 % by weight.The result of reacting 0.5 hour and 700 hours is listed in Table 1.
Embodiment 7
Adopt the method cacodyl oxide base thioether identical with embodiment 5, unlike, under the condition that the total filling amount of shaping HTS is constant, first load shaping hollow HTS, recharge shaping titanium-silicon molecular sieve TS-1, thus formation beds, wherein, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 1:1.Carry out the reaction of 760 hours, at the end of reaction, the concentration of ammoniacal liquor is 21 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 40 % by weight.The result of reacting 0.5 hour and 760 hours is listed in Table 1.
Embodiment 8
Adopt the method cacodyl oxide base thioether identical with embodiment 5, unlike, under the condition that the total filling amount of shaping HTS is constant, first load shaping hollow HTS, recharge shaping titanium-silicon molecular sieve TS-1, wherein, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 1:2.Carry out the reaction of 730 hours, at the end of reaction, the concentration of ammoniacal liquor is 22 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 41 % by weight.The result of reacting 0.5 hour and 730 hours is listed in Table 1.
Embodiment 9
Adopt the method cacodyl oxide base thioether identical with embodiment 5, unlike, under the condition that the total filling amount of shaping HTS is constant, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 8:1.Carry out the reaction of 840 hours, at the end of reaction, the concentration of ammoniacal liquor is 16 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 37 % by weight.The result of reacting 0.5 hour and 840 hours is listed in Table 1.
Embodiment 10
Adopt the method cacodyl oxide base thioether identical with embodiment 5, unlike, under the condition that the total filling amount of shaping HTS is constant, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 20:1.Carry out the reaction of 740 hours, at the end of reaction, the concentration of ammoniacal liquor is 21 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 42 % by weight.The result of reacting 0.5 hour and 740 hours is listed in Table 1.
Table 1
Embodiment 1 and 2 and comparative example 1 are compared and can find out, adopts method of the present invention desirable oxidation selectivity of product stably can be maintained higher level within the longer time, thus effectively extend the one way work-ing life of HTS.
Embodiment 2 and 3 and embodiment 4-10 are compared and can find out, hollow HTS and titanium-silicon molecular sieve TS-1 are combinationally used, and make hollow HTS be positioned at the upstream of titanium-silicon molecular sieve TS-1, that is: the beds of reactant first by being formed by hollow HTS is made, beds again by being formed by titanium-silicon molecular sieve TS-1, can further extending catalyst one way work-ing life.
Embodiment 1 and embodiment 2 are compared and can find out, using the quality of the raising liquid mixture neutral and alkali material as set-up procedure and the mass combination use improving oxygenant in liquid mixture, the one way work-ing life of the HTS as catalyzer can be extended further.
Embodiment 11-20 relates to following four kinds of catalyzer.
C1: (for volume average particle size is the spherical catalyst of 800 μm, density is 0.69g/cm to the shaping hollow HTS drawn off from propylene ring oxidation reaction process 3) carry out regenerating obtaining, this catalyzer contains the hollow HTS of 85 % by weight and the silicon oxide of 15 % by weight, and regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.The activity of regenerated catalyst be 30% (its activity be 96%) when fresh.
C2: (for volume average particle size is the spherical catalyst of 800 μm, density is 0.75g/cm to the shaping titanium-silicon molecular sieve TS-1 drawn off from propylene ring oxidation reaction process 3) carry out regenerating obtaining, this catalyzer contains the titanium-silicon molecular sieve TS-1 of 85 % by weight and the silicon oxide of 15 % by weight, and regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.The activity of regenerated catalyst be 30% (its activity be 95%) when fresh.
C3: the fresh shaping hollow HTS forming C1.
C4: the fresh shaping titanium-silicon molecular sieve TS-1 forming C2.
Embodiment 11
The present embodiment adopts reducing fixed-bed reactor, and these reducing fixed-bed reactor have the beds for loading HTS of two different inner diameters, is the internal diameter zone of transition of taper between two beds, wherein not loading catalyst.With liquid material flow direction in the reactor for benchmark, the beds being positioned at upstream is called the first beds, the beds being positioned at downstream is called the second beds, first beds and the equal loading catalyst C1 of the second beds, the weight ratio of the loaded catalyst in the loaded catalyst in the first beds and the second beds is 5:1, and the ratio of the internal diameter of the first beds and the internal diameter of the second beds is 2:1.
(be mixed with alkaline substance solution with methanol mixed to use using by dimethyl thioether, the hydrogen peroxide (providing using the form of the hydrogen peroxide of 27.5 % by weight) as oxygenant, the methyl alcohol as solvent and pyridine, in alkaline substance solution, the starting point concentration of pyridine is 12 % by weight) be mixed to form liquid mixture, the bottom of described liquid mixture from fixed-bed reactor is sent into, flows through the first beds and the second beds successively.Wherein, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:0.3, the mol ratio of dimethyl thioether and solvent methanol (not comprising the methyl alcohol in alkaline substance solution) is 1:20, the initial molar ratio of dimethyl thioether and pyridine is 1:0.0002, and the weight hourly space velocity (with the total amount of the HTS in the first beds and the second beds for benchmark) of dimethyl thioether is for 2.5h -1.First beds and the second reaction bed temperature are 35 DEG C, and the pressure-controlling in fixed-bed reactor is 0.5MPa.
The composition of the reaction mixture exported from reactor is monitored continuously, at dimethyl sulfoxide (DMSO) selectivity S in reaction process twith initial (reaction proceeds to 2 little sampling and measuring constantly) dimethyl sulfoxide (DMSO) selectivity S 0ratio S t/ S 0be 0.85≤S t/ S 0during <0.9 (, satisfy condition 1 time), the consumption (realized by the concentration improving pyridine in alkaline substance solution, the consumption of alkaline substance solution remains unchanged simultaneously) of pyridine in liquid mixture is improved until dimethyl sulfoxide (DMSO) selectivity S ' and initial dimethyl sulfoxide (DMSO) selectivity S with the amplitude in 0.01-10%/sky 0ratio S '/S 0be 0.9≤S '/S 0when≤1 (that is, satisfy condition 2 time), stop improving the quality of pyridine and the numerical value after being remained raising.
Carry out the reaction of 740 hours, at the end of reaction, in alkaline substance solution, the concentration of pyridine is 28 % by weight.The dimethyl sulfoxide (DMSO) selectivity that the reaction mixture being proceeded to 2 hours by reaction and obtained for 740 hours is determined and oxygenant effective rate of utilization are listed in table 2.
Comparative example 2
Adopt the method cacodyl oxide base thioether identical with embodiment 11, unlike, do not change the quality of pyridine in liquid mixture in reaction process.
The result of reacting 2 hours and 400 hours is listed in table 2.
Embodiment 12
Adopt the method cacodyl oxide base thioether identical with embodiment 11, unlike, the temperature of the first beds controls to be 35 DEG C, and the temperature of the second beds controls to be 25 DEG C.
Carry out the reaction of 770 hours, at the end of reaction, in alkaline substance solution, the concentration of pyridine is 26 % by weight.The dimethyl sulfoxide (DMSO) selectivity that the reaction mixture being proceeded to 2 hours by reaction and obtained for 770 hours is determined and oxygenant effective rate of utilization are listed in table 2.
Embodiment 13
Adopt the method cacodyl oxide base thioether identical with embodiment 11, unlike, the initial molar ratio of dimethyl thioether and hydrogen peroxide is 1:0.3, in reaction process, to satisfy condition for the 1st time 1 time, the quality of hydrogen peroxide in liquid mixture is improved (namely with the amplitude in 0.02-5%/sky, set-up procedure B) (realized by the concentration improving hydrogen peroxide in hydrogen peroxide, simultaneously the consumption of hydrogen peroxide remains unchanged) until satisfy condition 2 time, stop improving the quality of hydrogen peroxide and the numerical value after being remained rising; Satisfy condition the 2nd and 3 times 1 time, the consumption improving pyridine in liquid mixture with the amplitude in 0.01-10%/sky (is realized by the concentration improving pyridine in alkaline substance solution, the consumption of alkaline substance solution remains unchanged simultaneously) (namely, set-up procedure A) until satisfy condition 2 time, the quality of pyridine that tops out the numerical value after being remained rising, the rest may be inferred (namely, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, wherein, between adjacent twice set-up procedure B, twice set-up procedure A is carried out).
Carry out the reaction of 840 hours, at the end of reaction, in alkaline substance solution, the concentration of pyridine is 21 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 36 % by weight.The result of reacting 2 hours and 840 hours is listed in table 2.
Embodiment 14
Adopt the method cacodyl oxide base thioether identical with embodiment 13, unlike, the temperature of the first beds controls to be 50 DEG C, and the temperature of the second beds controls to be 35 DEG C.
Carry out the reaction of 870 hours, at the end of reaction, in alkaline substance solution, the concentration of pyridine is 20 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 34 % by weight.The result of reacting 2 hours and 870 hours is listed in table 2.
Embodiment 15
Adopt the method cacodyl oxide base thioether identical with embodiment 14, unlike, the catalyzer C2 of the catalyzer C1 equivalent in the second beds replaces.
Carry out the reaction of 980 hours, at the end of reaction, in alkaline substance solution, the concentration of pyridine is 18 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 35 % by weight.The result of reacting 2 hours and 980 hours is listed in table 2.
Embodiment 16
Adopt the method cacodyl oxide base thioether identical with embodiment 15, unlike, under the condition that catalyzer total filling amount remains unchanged, make the weight ratio of catalyzer C1 and catalyzer C2 be 10:1, the first beds and the ratio of the internal diameter of the second beds are 5:1 (internal diameter of the second beds is identical with embodiment 15).
Carry out the reaction of 980 hours, at the end of reaction, in alkaline substance solution, the concentration of pyridine is 17 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 35 % by weight.The result of reacting 2 hours and 980 hours is listed in table 2.
Embodiment 17
Adopt the method cacodyl oxide base thioether identical with embodiment 15, unlike, under the condition that the loadings of the first beds and the second beds is constant, the first beds and the ratio of the internal diameter of the second beds is made to be 1:1 (internal diameter of the second beds is identical with embodiment 15).
Carry out the reaction of 820 hours, at the end of reaction, in alkaline substance solution, the concentration of pyridine is 21 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 36 % by weight.The result of reacting 2 hours and 820 hours is listed in table 2.
Embodiment 18
Adopt the method cacodyl oxide base thioether identical with embodiment 15, unlike, under the condition that the loadings of the first beds and the second beds is constant, the first beds and the ratio of the internal diameter of the second beds is made to be 1:2 (internal diameter of the second beds is identical with embodiment 15).
Carry out the reaction of 780 hours, at the end of reaction, in alkaline substance solution, the concentration of pyridine is 22 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 36 % by weight.The result of reacting 2 hours and 780 hours is listed in table 2
Embodiment 19
Adopt the method cacodyl oxide base thioether identical with embodiment 15, unlike, the catalyzer C3 of catalyzer C1 equivalent replaces, and the catalyzer C4 of catalyzer C2 equivalent replaces.
Carry out the reaction of 880 hours, at the end of reaction, in alkaline substance solution, the concentration of pyridine is 23 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 34 % by weight.The result of reacting 2 hours and 880 hours is listed in table 2.
Embodiment 20
Adopt the method cacodyl oxide base thioether identical with embodiment 15, unlike, catalyzer C1 and catalyzer C2 all replaces with the catalyzer C3 of equivalent.
Carry out the reaction of 800 hours, at the end of reaction, in alkaline substance solution, the concentration of pyridine is 25 % by weight, and in hydrogen peroxide, the concentration of hydrogen peroxide is 37 % by weight.The result of reacting 2 hours and 800 hours is listed in table 2.
Table 2
Embodiment 15,17 and 18 is compared and can find out, make liquid mixture elder generation with lower superfacial velocity by being positioned at the beds of upstream, and then with higher superfacial velocity by being positioned at the beds in downstream, can one way work-ing life of extending catalyst further.
Embodiment 21
The catalyzer used in the present embodiment is for being undertaken regenerating by the shaping hollow HTS drawn off from phenol hydroxylation reaction process (for volume average particle size is the spherical catalyst of 250 μm) and obtain, this catalyzer contains the hollow HTS of 85 % by weight and the silicon oxide of 15 % by weight, and regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.The activity of regenerated catalyst be 40% (its activity be 96%) when fresh.
By catalyst loading in fixed-bed reactor, form beds, wherein, the quantity of beds is 1 layer.
By thioanisole, as the tertbutyl peroxide of oxygenant, (form being hybridly prepared into oxidizing agent solution with acetonitrile provides, in oxidizing agent solution, the starting point concentration of tertbutyl peroxide is 10 % by weight), (be hybridly prepared into alkaline substance solution with acetonitrile to use as the acetonitrile (not comprising the acetonitrile in oxidizing agent solution and alkaline substance solution) of solvent and Tetramethylammonium hydroxide, in alkaline substance solution, the starting point concentration of Tetramethylammonium hydroxide is 20 % by weight) be mixed to form liquid mixture, liquid mixture to be sent in fixed-bed reactor and to flow through beds.Wherein, the mol ratio of thioanisole and tertbutyl peroxide is 1:1, the mol ratio of thioanisole and solvent acetonitrile (not comprising the acetonitrile in oxidizing agent solution and alkaline substance solution) is 1:8, the initial molar ratio of thioanisole and Tetramethylammonium hydroxide is 1:0.00005, and the weight hourly space velocity of thioanisole is 10h -1.Temperature in beds is 70 DEG C, controls the original pressure in fixed-bed reactor for 2.5MPa.
The composition of the reaction mixture exported from reactor is monitored continuously, at first time benzene first sulfoxide selectivity S in reaction process twith initial (reaction proceeds to 2 little sampling and measuring constantly) benzene first sulfoxide selectivity S 0ratio S t/ S 0be 0.85≤S t/ S 0during <0.9 (, satisfy condition 1 time), the mass concentration (realized by the concentration improving Tetramethylammonium hydroxide in alkaline substance solution, the consumption of alkaline substance solution remains unchanged simultaneously) of Tetramethylammonium hydroxide in liquid mixture is improved until benzene first sulfoxide selectivity S ' and initial benzene first sulfoxide selectivity S with the amplitude in 0.01-10%/sky 0ratio S '/S 0be 0.9≤S '/S 0when≤1 (that is, satisfy condition 2 time), stop improving the mass concentration of Tetramethylammonium hydroxide and the numerical value (that is, set-up procedure A) after remaining raising, to satisfy condition for the 2-4 time 1 time, improve the quality of tertbutyl peroxide in liquid mixture with the amplitude in 0.02-5%/sky (to be realized by the concentration improving tertbutyl peroxide in oxidizing agent solution, the consumption of corresponding reduction oxidizing agent solution simultaneously, remain unchanged to make the mol ratio of thioanisole and tertbutyl peroxide) until satisfy condition 2 time, stop improving the quality of tertbutyl peroxide and numerical value after remaining raising (namely, set-up procedure B), the rest may be inferred (namely, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, wherein, three set-up procedure B are carried out) between adjacent twice set-up procedure A.
Carry out the reaction of 970 hours, at the end of reaction, in alkaline substance solution, the concentration of Tetramethylammonium hydroxide is 24 % by weight, and in oxidizing agent solution, the concentration of tertbutyl peroxide is 32 % by weight.The result of reacting 2 hours and 970 hours is listed in table 3.
Table 3
The result of embodiment 4,11-18 and 21 confirms, draw off agent as catalyzer even if use, method of the present invention also can obtain good reaction effect, and can obtain higher oxygenant effective rate of utilization, achieves effective recycling of waste catalyst.

Claims (15)

1. a sulfide oxidation method, under the method is included in oxidation reaction condition, a kind of liquid mixture is contacted with HTS, described liquid mixture contains thioether, at least one oxygenant, at least one alkaline matter and optional at least one solvent, wherein, desirable oxidation selectivity of product drop to satisfy condition 1 time, the method also comprises carries out set-up procedure, until desirable oxidation selectivity of product rises to when satisfying condition 2, stop described set-up procedure
Desirable oxidation selectivity of product S under condition 1, sometime t twith initial target oxidation products selectivity S 0ratio S t/ S 0be 0.85≤S t/ S 0<1;
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation products selectivity S 0ratio S '/S 0be 0.9≤S '/S 0≤ 1;
Described set-up procedure is the combination of set-up procedure A or set-up procedure A and set-up procedure B,
Set-up procedure A: the quality improving described liquid mixture neutral and alkali material;
Set-up procedure B: the quality improving oxygenant in described liquid mixture.
2. method according to claim 1, wherein, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, and carry out set-up procedure A at least one times between adjacent twice set-up procedure B; Or, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, and at least carry out a set-up procedure B between adjacent twice set-up procedure A.
3. method according to claim 1 and 2, wherein, in condition 1, S t/ S 0<0.9.
4. method according to claim 1, wherein, the mol ratio of described alkaline matter and thioether is in the scope of 0.00001-0.1:1; The mol ratio of described oxygenant and thioether is in the scope of 0.1-5:1.
5. the method according to claim 1 or 4, wherein, improves the quality of alkaline matter with the amplitude in 0.01-10%/sky; And/or
The quality of oxygenant in described liquid mixture is improved with the amplitude in 0.02-5%/sky.
6. method according to claim 1, wherein, described HTS is seated in the beds of fixed-bed reactor, described beds comprises the first beds and the second beds, with the flow direction of liquid mixture for benchmark, described first beds is positioned at the upstream of described second beds, and the HTS that the HTS of described first beds filling and described second beds load is identical or different.
7. method according to claim 6, wherein, the HTS of described first beds filling is hollow HTS, the crystal grain of described hollow HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P 0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm; And
The HTS of described second beds filling is titanium-silicon molecular sieve TS-1.
8. the method according to claim 6 or 7, wherein, the weight ratio of the HTS that the HTS of described first beds filling and described second beds load is 0.5-20:1, is preferably 2-10:1.
9. according to the method in claim 6-8 described in any one, wherein, described liquid mixture flows through the superfacial velocity of the first beds is v 1, the superfacial velocity flowing through the second beds is v 2, v 1< v 2; Preferably, v 2/ v 1=1.5-10; More preferably, v 2/ v 1=2-5.
10. according to the method in claim 6-9 described in any one, wherein, the residence time of described liquid mixture in the first beds is T 1, the total residence time in beds is T, T 1/ T=0.2-0.96; Preferably, T 1/ T=0.5-0.85.
11. according to the method in claim 6-10 described in any one, and wherein, the temperature of described first beds is higher than the temperature of described second beds; Preferably, the temperature of described first beds is than the temperature height 5-30 DEG C of described second beds.
12. according to the method in claim 1 and 6-11 described in any one, and wherein, described contact is carried out at the temperature of 0-120 DEG C.
13. according to the method in claim 1 and 6-12 described in any one, wherein, at least part of HTS be through regeneration the reaction unit using HTS as catalyzer draw off agent, described in draw off agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off in agent one or more.
14. according to the method in claim 1,2 and 4-7 described in any one, and wherein, described oxygenant is superoxide.
15. according to the method in claim 1,2 and 4-7 described in any one, and wherein, described thioether is dimethyl thioether and/or thioanisole.
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